U.S. patent number 5,134,218 [Application Number 07/711,001] was granted by the patent office on 1992-07-28 for hydroxy-functional poly(amide ethers) as thermoplastic barrier resins.
This patent grant is currently assigned to The Dow Chemical Company. Invention is credited to David J. Brennan, Jerry E. White.
United States Patent |
5,134,218 |
Brennan , et al. |
July 28, 1992 |
**Please see images for:
( Certificate of Correction ) ** |
Hydroxy-functional poly(amide ethers) as thermoplastic barrier
resins
Abstract
Poly(hydroxy amide ethers) which exhibit high barrier properties
are prepared by contacting one or more amide-containing bisphenols
and an epihalohydrin. These polymers are suitable for use in the
manufacture of articles such as rigid containers and flexible films
exhibiting high barrier to oxygen transmission in moist
environments.
Inventors: |
Brennan; David J. (Midland,
MI), White; Jerry E. (Midland, MI) |
Assignee: |
The Dow Chemical Company
(Midland, MI)
|
Family
ID: |
24856387 |
Appl.
No.: |
07/711,001 |
Filed: |
June 6, 1991 |
Current U.S.
Class: |
528/99;
528/104 |
Current CPC
Class: |
C08G
59/063 (20130101); C08G 59/28 (20130101); C08G
69/40 (20130101) |
Current International
Class: |
C08G
69/00 (20060101); C08G 69/40 (20060101); C08G
59/28 (20060101); C08G 59/06 (20060101); C08G
59/00 (20060101); C08G 059/00 (); C08G 065/08 ();
C08G 065/14 () |
Field of
Search: |
;528/99,104 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bleutge; John C.
Assistant Examiner: Krass; Frederick
Claims
What is claimed is:
1. A thermoplastic barrier polymer having aromatic ether moieties
and amide moieties in its backbone chain and pendent hydroxyl
moieties and having repeating units represented by the formula:
##STR8## wherein each Ar is independently a divalent aromatic
moiety, each R.sup.1 is independently a predominantly
hydrocarbylene moiety, divalent aromatic moiety, or divalent
heteroaromatic moiety, each R.sup.2 is independently hydrogen or a
monovalent aliphatic moiety and n is 10 to 1000.
2. The polymer of claim 1 wherein Ar is arylene or substituted
arylene wherein the substituent is alkyl, aryl, halo, nitro, or
cyano; R.sup.1 is predominantly hydrocarbylene chosen from (1)
alkylene which has from 1 to about 10 carbons which may contain a
heteroatomic moiety chosen from oxygen, sulfur, sulfonyl, or
sulfoxyl or (2) arylene which has from 5 to 25 carbons, may contain
a heteroatomic moiety and may be substituted with alkyl, alkoxy,
halo, nitro, or cycloalkyl groups; and R.sup.2 is hydrogen or a
hydrocarbyl or substituted hydrocarbyl wherein the substituent(s)
is a monovalent moiety which is inert in the reactions used to
prepare the polymer.
3. The polymer of claim 1 prepared by contacting one or more
amide-containing bisphenols and an epihalohydrin.
4. The polymer of claim 1 prepared by contacting one or more
amide-containing bisphenols and an epihalohydrin.
5. The polymer of claim 2 having repeating units represented by the
formula: ##STR9##
6. The polymer of claim 2 having repeating units represented by the
formula: ##STR10##
7. The polymer of claim 2 having repeating units represented by the
formula: ##STR11##
8. The polymer of claim 3 wherein the amide-containing bisphenol is
selected from the group consisting of
N,N'-bis(3-hydroxyphenyl)adipamide,
N,N'-bis(3-hydroxyphenyl)glutaramide and
.alpha.,.alpha.'-bis(4-hydroxybenzamido)-1,3-xylene.
9. The polymer of claim 3 wherein the epihalohydrin is selected
from the group consisting of epichlorohydrin, epibromohydrin, and
epiiodohydrin.
10. The polymer of claim 1 in the form of a barrier film.
11. The polymer of claim 1 in the form of a barrier container.
12. The polymer of claim 1 in the form of a barrier coating.
Description
BACKGROUND OF THE INVENTION
This invention relates to thermoplastic polymers having aromatic
ether moieties in the backbone chain and pendant hydroxyl moieties
and to articles prepared from such polymers.
Hydroxyphenoxyether polymers are known to be useful in the
fabrication of articles exhibiting barrier properties. See. for
example, Reinking et al, J. Poly Sci., Vol. 7, pp. 2135-2144, pp.
2145-2152 and pp. 2153-2160 (1963) and Encyclopedia of Polymer
Science and Technology, Vol. 10, pp. 111-122. Such polymers
generally have only moderate oxygen barrier. i.e., they generally
exhibit oxygen transmission rates of 2 to 75 cm.sup.3 -mil/100
in.sup.2 -atm-day.
In view of the limited barrier properties of the prior art polymers
having pendant hydroxyl moieties and phenoxyether moieties, it
would be highly desirable to provide a polymer having a genuinely
high barrier (i.e., oxygen transmission rate less than 1 cm.sup.3
-mil/100 in.sup.2 -atm-day) to oxygen. Polymers that retain such
high barrier in both dry and moist environments would be especially
desirable.
SUMMARY OF THE INVENTION
The present invention is, in one aspect, a normally solid
thermoplastic barrier polymer having aromatic ether moieties and
amide moieties in the backbone chain and pendant hydroxyl moieties
and is prepared by reacting one or more amide-containing bisphenols
and an epihalohydrin. Surprisingly, the polymer of this invention,
hereinafter called a hydroxy-functional poly(amide ether), exhibits
thermoplastic character and excellent barrier to oxygen. By
"normally solid" it is meant that the polymer is solid at ambient
temperatures, e.g.. 15.degree.-35.degree. C.
In another aspect, this invention is a container suitable for
packaging oxygen-sensitive materials wherein the container is
fabricated of the hydroxy-functional poly(amide ether). In yet a
further aspect, this invention is a substantially impermeable film
or coating of the polymer.
For the purposes of this invention, the term "barrier polymer"
means that the polymer exhibits an oxygen transmission rate which
is less than 2, preferably less than 1, cubic centimeters-mil/100
inch.sup.2 atmosphere-day.
In addition to their use as barrier containers and films, the
polymers of this invention are also useful as molding, extrusion
and casting resins.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
Preferably, the poly(hydroxy amide ether) has repeating units
represented independently by the formulae: ##STR1## wherein each Ar
is independently a divalent aromatic moiety, each R.sup.1 is a
predominantly hydrocarbylene moiety, such as a divalent aromatic
moiety, or divalent heteroaromatic moiety, each R.sup.2 is hydrogen
or a monovalent aliphatic moiety and n is 10 to 1000.
"Predominantly hydrocarbylene" is defined as a divalent radical
that is predominantly hydrocarbon, but which optionally contains a
minor amount of heteroatomic moiety such as oxygen, sulfur, imino,
sulfonyl, sulfoxyl, and the like.
In the more preferred polymers, Ar is arylene or substituted
arylene wherein the substituent may be alkyl, aryl, halo, nitro, or
cyano: R.sup.1 is predominantly hydrocarbylene such as (1) alkylene
or cycloalkylene which has from 1 to about 10 carbons which may
contain a heteroatomic moiety such as oxygen, sulfur, sulfonyl, or
sulfoxyl and (2) arylene which has from 5 to 25 carbons, may
contain a heteroatomic moiety and may be substituted with alkyl,
alkoxy, halo, nitro, or cycloalkyl groups: and R.sup.2 is hydrogen
or a hydrocarbyl or substituted hydrocarbyl wherein hydrocarbyl is
a monovalent hydrocarbon such as alkyl, cycloalkyl, aralkyl, or
aryl and the substituent(s) is a monovalent moiety which is inert
in the reactions used to prepare the poly(hydroxy amide-ethers).
Examples of such substituents include cyano, halo, amido, hydroxy
and hydroxyalkyl.
In the most preferred poly(hydroxy amide ethers), Ar is phenylene
or substituted phenylene wherein the substituent is alkyl, alkoxy,
halo, or nitro, with phenylene being especially preferred; R.sup.1
is (1) alkylene having from 1 to 10 carbons such as methylene,
ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene,
n-octylene; (2) alkyleneoxyalkylene such as methylene,
ethyleneoxyethylene; (3) alkylene thioalkylene such as
ethylenethioethylene or alkylenesulfonylalkylene such as
ethylenesulfonylethylene; (4) alkyleneoxyaryloxyalkylene such as
ethyleneoxyphenoxyethylene: (5) alkylenearylalkylene such as
methylenephenylmethylene; or (6) arylene such as phenylene or
substituted arylene such as halophenylene: R.sup.2 is hydrogen or
alkyl having from 1 to 4 carbons such as methyl, ethyl, propyl, and
butyl, with hydrogen being especially preferred, and n is 100 to
400.
The poly(hydroxy amide ethers) are preferably prepared by
contacting a bis(hydroxyphenylamido)alkane or arene, or a
combination of 2 or more of these compounds, hereinafter referred
to as amide-containing bisphenols, such as
N,N'-bis(3-hydroxyphenyl) adipamide or N,N'-bis(3-hydroxyphenyl)
glutaramide, with an epihalohydrin under conditions sufficient to
cause the hydroxyl moieties to form ether linkages and pendant
hydroxyl moieties. Conditions conventionally employed in the
reaction of epoxides with phenols to form ether linkages are
suitably employed in preparing the resins of this invention.
Examples of such suitable conditions are set forth in U.S. Pat. No.
3.305,528 which is hereby incorporated by reference in its
entirety. Preferred conditions for preparing such resins are set
forth in the following working examples.
The amide-containing bisphenol is prepared by contacting a suitable
diacid or diacid halide with a substantial excess of an aminoarenol
under conditions sufficient to cause reaction of the amine moieties
with the acid halide moieties to form amide moieties. Examples of
diacids and diacid halides that are suitably employed include acids
and acid halides, preferably chlorides of the following acids:
oxalic, adipic, malonic, succinic, glutaric, fumaric, maleic,
pimelic. suberic, azelaic, sebacic, terephthalic, isophthalic and
phenylenediacetic. Examples of aminoarenols suitably employed
include the following: aminophenols such as p-aminophenol and
m-aminophenol, aminonaphthols and other aminohydroxyarenes.
Conditions conventionally employed for the reaction of acid
chlorides with amines to form amides are suitably employed to form
the amide-containing bisphenols of this invention. Examples of such
suitable conditions are set forth according to J. Preston,
J.Polym.Sci., Vol. 8, p. 3135-3144 (1970).
Alternatively, the amide-containing bisphenol can be prepared by
contacting a suitable diamine with a hydroxybenzoic acid derivative
such as a hydroxybenzoic acid ester, an acetoxybenzoyl halide, or
acetoxybenzoic acid, under conditions sufficient to cause reaction
of the amine group with the carboxylic acid or carboxylic acid
derivative to form amide moieties, followed by removal of the
acetyl group in the case of the acetoxy species. Examples of
diamines that are suitably employed include ethylenediamine,
1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine,
hexamethylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine,
and m-xylylenediamine. Examples of hydroxybenzoic acid derivatives
that can be used include methyl 4-hydroxybenzoate, ethyl
4-hydroxybenzoate, phenyl 4-hydroxybenzoate, methyl salicyclate,
phenyl salicylate, 4-acetoxybenzoyl chloride, 4-acetoxybenzoic
acid, and other derivatives of carboxyhydroxyarenes. Preferred
conditions for preparing the amide-containing bisphenols are set
forth hereafter in the working examples.
Suitable epihalohydrins include, for example, epichlogohydrin,
epibromohydrin, epiiodohydrin, methyl epichlorohydrin,
methylepibromohydrin, methylepiiodohydrin, ethylepichlorohydrin,
ethylepibromohydrin, ethylepiiodohydrin and mixtures thereof.
The barrier containers, films and coatings of this invention are
fabricated from the hydroxy-functional poly(amide-ether) using
conventional fabricating techniques for normally solid,
thermoplastic polymers such as extrusion, compression molding,
thermoforming, injection molding and similar fabrication techniques
commonly employed to produce such articles.
The following working examples are given to illustrate the
invention and should not be construed as limiting its scope. Unless
otherwise indicated, all parts and percentages are by weight.
EXAMPLE 1
A. Preparation of N,N'-bis(3-hydroxyphenyl)adipamide
A solution of adipoyl chloride (5.5 g, 0.03 mol) in dry
tetrahydrofuran (THF, 50 mL) is added dropwise to a magnetically
stirred solution of 3-aminophenol (13.0 g, 0.12 mol) in 150 mL of
THF. A precipitate forms after 10-15 minutes and is collected by
filtration, washed with water, washed with a mixture of water and
tetrahydrofuran and recrystallized from an ethanol/water mixture.
Analysis of the resulting 8.86 g of white solid indicates it to
have the following structure: ##STR2##
Preparation of N,N'-bis(3-hydroxyphenyl)glutaramide
A solution of glutaryl chloride (42.25 g, 0.25 mol) in dry THF (300
mL) is added dropwise to a magnetically stirred solution of
g-aminophenol (110.4 g. 1.01 mol) in 1000 mL of THF. After stirring
at 25.degree. C. for 18 hours, the solution is heated to 66.degree.
C. for 4 hours, then cooled to 25.degree. C. Precipitated
3-aminophenol hydrochloride is collected by filtration and solvent
is removed from the resulting filtrate under reduced pressure to
yield an oil. The oil is poured into water, which causes
precipitation of an amber-colored solid which is recrystallized
twice from an ethanol/water mixture to yield 56.1 g of an off-white
solid with the following structure: ##STR3##
C. Preparation of
.alpha.,.alpha.'-bis(4-hydroxybenzamido)-1,3-xylene
A solution of m-xylylenediamine (10.22 g, 0.0750 mol) and
triethylamine (30.4 g, 0.30 mol) in dry THF (50 ml) is added to a
mechanically stirred solution of 4-acetoxybenzoyl chloride (29.79
g, 0.15 mol) in dry tetrahydrofuran (300 mL) which caused a
precipitate to form immediately. On completion of addition, the
mixture is stirred for 16 hours at 25.degree. C., then the
precipitated solid is collected by filtration. The solid is washed
with water and is treated with 35 mL of 5N NaOH (0.175 mol) in 400
mL of boiling 1:1 ethanol/water for two hours. The solution is
acidified with 15 mL of concentrated HCl and allowed to cool, which
causes a white solid to form. The solid is recrystallized twice
from an ethanol/water mixture to yield 20.8 g of a white solid that
is analyzed by proton and carbon-13 NMR spectroscopy and determined
to have the following structure: ##STR4##
Preparation of Polymer 1a
To a 100 mL polymerization kettle is added
N,N'-bis(3-hydroxyphenyl)glutaramide (15.62 g, 0.050 mol), ethanol
(30 mL), epichlorohydrin (4.63 , 0.050 mol), and sodium hydroxide
(2.00 g, 0.050 mol) dissolved in water (30 mL). The flask is fitted
with a top which contained a thermometer, an overhead mechanical
stirrer shaft, and a nitrogen inlet adapter. The contents of the
flask are stirred at 25.degree. C. under nitrogen for 17 hours,
after which more sodium hydroxide (0.30 g, 0.0075 mol) in water (5
mL) is added to the reaction mixture The contents of the flask are
then heated at 80 to 90.degree. C. for eight hours, after which
time a polymeric material precipitates from solution. The polymeric
mass is superficially washed with water, is dissolved in DMF (75
mL), then is precipitated into a cold solution of 3:1
methanol/water (400 mL) in a high speed blender. After washing with
methanol (100 mL) and water (100 mL), the off-white polymer is
redissolved in 100 mL of THF/water (95/5) to which acetic acid (10
mL) is added. The polymer is precipitated and washed a second time,
then is dried in vacuo at 80.degree. C. for 24 hours. The polymer
has repeating units represented by the formula: ##STR5##
E. Preparation of Polymer 1b
To a 500 mL polymerization kettle is added
N,N'-bis(3-hydroxyphenyl)adipamide (82.1 g, 0.250 mol),
epichlorohydrin (23.13 g, 0.250 mol), propylene glycol monophenyl
ether (150 mL), and sodium hydroxide (10.00 g. 0.250 mol) dissolved
in water (150 mL). The flask is fitted with a top which contained a
thermometer, an overhead mechanical stirrer shaft and a nitrogen
inlet adapter. The contents of the flask are stirred at 25.degree.
C. under nitrogen for 16 hours. Additional sodium hydroxide (1.50
g, 0.0375 mol) in water (20 mL) is added to the reaction mixture.
The contents of the flask are then heated at 95.degree. C. for 7
hours, after which time the viscosity of the reaction mixture
increases. The mixture is cooled to 25.degree. C. and the
non-polymeric supernatant liquid is decanted. The polymeric mass is
superficially washed with water several times and is dissolved in
DMF (200 mL). The polymer is precipitated into a cold solution of
3:1 methanol/water (2 L) in a high speed blender, then is washed
with methanol (1 L) and water (1 L). The off-white polymer is
collected via filtration, is redissolved in wet THF (500 mL), and
is precipitated a second time as described previously. The polymer
is washed by stirring in 50% aqueous methanol overnight, is
collected via filtration, is air-dried, and then is dried in vacuo
at 80.degree. C. for 24 hours. The polymer has repeating units
represented by the formula: ##STR6##
F. Preparation of Polymer 1c
To a 100 mL polymerization kettle is added
.alpha.,.alpha.'-bis(4-hydroxybenzamido)-1,3-xylene (11.29 g, 0.030
mol), propylene glycol monophenyl ethel (35 mL). epichlorohydrin
(2.87 g, 0.030 mol), and sodium hydroxide (1.20 g, 0.030 mol)
dissolved in water (10 mL). The flask is fitted with a top which
contained a thermometer, an overhead mechanical stirrer shaft, and
a nitrogen inlet adapter. The contents of the flask are stirred at
25.degree. C. under nitrogen for 16 hours, after which time more
sodium hydroxide (0.18 g, 0.0045 mol) in water (3 mL) is added to
the reaction mixture. The contents of the flask are then heated at
95.degree. C. for three hours, after which time more propylene
glycol monophenyl ether (10 mL) is added. The mixture is heated at
95.degree. C. for an additional six hours, during which time a
polymeric material precipitates from solution. The polymer is
dissolved in DMF and precipitates into a cold solution of 3:1
methanol/water (400 mL) in a high speed blender. After washing with
methanol (100 mL) and water (100 mL). the polymer is redissolved in
100 mL of DMF. After a second precipitation and washing, the
polymer is then dried in vacuo at 80.degree. C. for 25 hours. The
polymer has repeating units represented by the formula:
##STR7##
Q. Barrier Testing
Specimens (10 cm.times.10 cm .times.b 0.013 cm) for oxygen barrier
evaluations are prepared by compression molding samples (3.5 g) of
Polymers 1a, 1b and 1c between Teflon sheets in a brass template at
200.degree. C. to 250.degree. C. at 500 psi (3.5 mPa) for 8-10
minutes, then at 40,000 psi (275 mFa) for 2-4 minutes and then
cooled at 40,000 psi (275 mPa) for 10 minutes. Oxygen transmission
rates are then measured for the samples at 23.degree. C. in
accordance with ASTM method D-3985-81.
The yield, inherent viscosity (ninh), glass transition temperature
(T.sub.g), crystalline melting temperature (T.sub.m) and oxygen
transmission rate (OTR) at 70%-80% relative humidity of O.sub.2
data are given in Table 1.
TABLE I ______________________________________ Oxygen Poly- Yield
.sup..eta. inh Tg Tm Transmission Rate.sup.b mer (%) (dL/g).sup.a
(.degree.C.) (.degree.C.) OTR.sup.c RH (%).sup.d
______________________________________ 1 a 65 0.54 105 -- 0.11
74-80 1 b 81 0.44 107 159 0.19 70-80 1 c 62 0.43 142 -- 0.51 59-61
______________________________________ .sup.a Concentration of 0.25
g/50 mL in DMF at 25.degree. C. .sup.b ASTM method D398581 .sup.c
Oxygen transmission rate (OTR) in cc .multidot. mil/100 in.sup.2
.multidot. atm .multidot. day .sup.d Relative Humidity (RH) of
oxygen used to determine OTR.
As evidenced by the data in Table 1, the polymers of this invention
exhibit excellent barrier to oxygen transmission in a wet
environment.
* * * * *